Positive photosensitive resin compositions and semiconductor device

ABSTRACT

The present invention provides a positive-working photosensitive resin composition with high sensitivity that gives a pattern having a high resolution and a high film thickness retention rate. In other words, the present invention provides a positive-working photosensitive resin composition comprising 100 parts by weight of a polyamide and 1 to 50 parts by weight of a photosensitive material, that is, a 1,2-naphthoquinone-2-diazide-5-sulfonate ester compound or a 1,2-naphthoquinone-2-diazide-4-sulfonate ester compound of a phenol compound. In addition, the present invention provides a positive-working photosensitive resin composition comprising 100 parts by weight of a polyamide, 1 to 50 parts by weight of a photosensitive material, that is, a 1,2-naphthoquinone-2-diazide-5-sulfonate ester compound or a 1,2-naphthoquinone-2-diazide-4-sulfonate ester compound of a phenol compound and 1 to 30 parts by weight of a phenol compound. Furthermore, the present invention provides a semiconductor device manufactured by using said positive-working photosensitive resin composition.

FIELD OF THE INVENTION

[0001] The present invention relates to a positive-workingphotosensitive resin composition to be used for a surface protectionfilm of a semiconductor element, particularly a positive-workingphotosensitive resin composition with high sensitivity that gives apattern of high resolution and a high film thickness retention rate[(film thickness after development)/(film thickness beforedevelopment)×100] even in an increased film thickness. In addition, thepresent invention relates to a semiconductor device manufactured byusing said positive-working photosensitive resin composition.

BACKGROUND OF THE INVENTION

[0002] A polyimide resin having high heat resistance, excellentelectrical and mechanical properties and the like was conventionallyused for a surface protection film or an interlayer insulating film of asemiconductor element. However, a resin of further improved performancehas been lately required to satisfy the requirement for markedimprovement in resistance against repeated heat or thermal shock due tohigher integration and larger scale of a semiconductor element, thinningand down-sizing of a package, shift to surface mounting by reflow ofsolder and the like.

[0003] On the other hand, a technology to give photosensitivity to apolyimide resin itself has lately drawn attention, bringing about, forinstance, a photosensitive polyimide resin represented by the formula(7) below.

[0004] Using the above polyimide resin poses a problem in safety andhandling due to necessity of spraying a solvent such asN-methyl-2-pyrrolidone in development, while a part of procedures tomake a pattern can be simplified resulting in shorter process andimproved yield. Therefore, a positive-working photosensitive resin thatcan be developed by an aqueous solution of an alkali has been latelyexploited. For instance, a positive-working photosensitive resincomprising a polybenzoxazole precursor as a base polymer and adiazoquinone compound as a photosensitive material has been disclosed inJP-B-1-46862. This resin has high heat resistance, superior electricalproperties and fine processability, and a potential of resin not onlyfor wafer coating but also for interlayer insulation. With regard to adevelopment mechanism of this positive-working photosensitive resin, adiazoquinone compound in an exposed area is subjected to a chemicalchange to become soluble in an aqueous solution of an alkali, while thediazoquinone compound in an unexposed area remains insoluble in theaqueous solution of the alkali. Utilizing the difference of solubilitybetween the exposed area and the unexposed area, a pattern of coatingfilm only in the unexposed area can be obtained by dissolving andremoving the resin in the exposed area.

[0005] In an actual use of these photosensitive resins, sensitivity ofthe photosensitive resins is especially of significance. Low sensitivityrequires a longer exposure time resulting in a lower throughput. On theother hand, if, for instance, a base polymer with a lower molecularweight is used in an attempt to improve sensitivity of a photosensitiveresin, problems such as failing to obtain a desired film thickness orcollapse of a pattern shape arise due to increased loss of filmthickness in an unexposed area during development. Thus, development ofa photosensitive resin of high sensitivity having such properties asdescribed above has been greatly desired. In addition, since a thicknessof resin film tends to increase from conventional about 5 to 7 μm toabout 10 to 20 μm, a photosensitive resin with high sensitivity even inan increased thickness has been expected to be developed.

DISCLOSURES OF THE INVENTION

[0006] An object of the present invention is to provide apositive-working photosensitive resin composition with high sensitivitythat gives a pattern having a high resolution and a high film thicknessretention rate [(film thickness after development)/(film thicknessbefore development)×100]. Further, the present invention provides apositive-working photosensitive resin composition with high sensitivitythat is free from the above problems even with an increased filmthickness.

[0007] The present invention relates to a positive-workingphotosensitive resin composition comprising 100 parts by weight of apolyamide (A) represented by the general formula (1):

[0008] [wherein, X is a cyclic compound group of 2 to 4 valences thatmay have a hydroxyl group or a group wherein a hydrogen atom of ahydroxyl group is replaced with an organic group having 1 to 20 carbonatoms; Y is a cyclic compound group of 2 to 4 valences that may have ahydroxyl group, a group wherein a hydrogen atom of a hydroxyl group isreplaced with an organic group having 1 to 20 carbon atoms, a carboxylgroup or a group wherein a hydrogen atom of a carboxyl group is replacedwith an organic group having 1 to 20 carbon atoms;

[0009] Z is:

[0010] (wherein, each of R1 and R2 is a bivalent organic group; each ofR3 and R4 is a univalent organic group); a and b each shows a molarfraction; a+b=100% by mole; a=60 to 100% by mole; and b=0 to 40% bymole)];

[0011] and 1 to 50 parts by weight of a photosensitive material (B),that is a 1,2-naphthoquinone-2-diazide-5-sulfonate ester compound or a1,2-naphthoquinone-2-diazide-4-sulfonate ester compound of a phenolcompound having a skeletal structure represented by the formula (5):

[0012] Further, the present invention relates to a positive-workingphotosensitive resin composition further comprising 1 to 30 parts byweight of a phenol compound represented by the general formula (6) basedon 100 parts by weight of the polyamide (A) represented by the generalformula (1) in the above positive-working photosensitive resincomposition:

[0013] (wherein, each of R11, R12, R13 and R14 is selected from ahydrogen atom, a halogen atom, an alkyl group, an alkoxy group and acycloalkyl group, and may be the same or different from each other; p isan integer of 0 to 3; q is an integer of 0 to 3; p+q≧2; R15 is selectedfrom a single bond, a methylene group, an alkylene group, an oxygenatom, a carbonyl group, a carbonyl ether group, a sulfur atom, asulfonyl group and an azo group.)

[0014] A more preferable embodiment is the above positive-workingphotosensitive resin composition wherein X in the polyamide representedby the general formula (1) is selected from the groups shown below; Y inthe polyamide represented by the general formula (1) is selected fromthe groups shown below; and a terminal group of the polyamiderepresented by the general formula (1) is selected from E below, thatis, an aliphatic group or a cyclic compound group having at least onegroup of an alkenyl group or an alkynyl group.

[0015] (wherein, each of R₁₆is selected from a hydrogen atom, an alkylgroup, an alkoxy group, an alkyl ester group and a halogen atom, and maybe the same or different from each other; r is an integer of 0 to 2.)

[0016] (wherein, each of R₁₆ is selected from a hydrogen atom, an alkylgroup, an alkoxy group, an alkyl ester group and a halogen atom, and maybe the same or different from each other; r is an integer of 0 to 2.)

[0017] In addition, the present invention relates to a semiconductordevice manufactured by using the above positive-working photosensitiveresin composition, which is obtained by applying the abovepositive-working photosensitive resin composition on a semiconductorelement so that a film thickness of the above positive-workingphotosensitive resin composition after dehydration and cyclizationbecomes 0.1 to 30 μm, followed by prebaking, exposing, developing andheating.

DETAILED DESCRIPTION OF THE INVENTION

[0018] The polyamide resin represented by the general formula (1) isobtained by reacting a diamine or a bis(aminophenol) or the like havinga structure of X, a silicone-diamine having a structure of Z which isadded if necessary, and a tetracalboxylic anhydride, a dicarboxylicacid, a dicarboxylic dichloride, a dicarboxylic acid derivative or thelike having a structure of Y. Incidentally, in the case of adicarboxylic acid, an activated ester-type derivative of dicarboxylicacid reacted in advance with 1-hydroxy-1,2,3-benzotriazole or the likemay be used so as to enhance a reaction yield and the like. Thispolyamide resin is dehydrated and cyclized by heating at about 300 to400° C. to obtain a heat-resistant resin in a form of a polyamide or apolybenzoxazole or a copolymer of both polymers.

[0019] X of the polyamide resin represented by the general formula (1)of the present invention is, for instance:

[0020] (wherein, A is —CH₂—, —C(CH₃)₂—, —O—, —S—, —SO₂—, —CO—, —NHCO—,—C(CF₃)₂— or a single bond; each of R₁₆ is selected from a hydrogenatom, an alkyl group, an alkoxy group, an alkyl ester group and ahalogen atom, and may be the same or different from each other; r is aninteger of 0 to 2), but is not limited to these groups.

[0021] Particularly preferable X among these is selected from:

[0022] (Each of R₁₆ is selected from a hydrogen atom, an alkyl group, analkoxy group, an alkyl ester group and a halogen atom, and may be thesame or different from each other; r is an integer of 0 to 2) and two ormore kinds of these may be used.

[0023] Y of the polyamide resin represented by the general formula (1)is, for instance:

[0024] (wherein, A is —CH₂—, —C(CH₃)₂——O—, —S—, SO₂—, —CO—, —NHCO—,—C(CF₃)₂— or a single bond; R₁₆is selected from a hydrogen atom, analkyl group, an alkoxy group, an alkyl ester group and a halogen atom,and may be the same or different from each other; r is an integer of 0to 2), but is not limited to these groups.

[0025] Particularly preferable Y among these is selected from:

[0026] (wherein each of R₁₆ is selected from a hydrogen atom, an alkylgroup, an alkoxy group, an alkyl ester group and a halogen atom, and maybe the same or different from each other; r is an integer of 0 to 2),and two or more kinds of these may be used.

[0027] From the viewpoint of storage stability of the positive-workingphotosensitive resin composition of the present invention, after thepolyamide resin is synthesized by reacting a diamine or abis(aminophenol) or the like having a structure of X, a silicone-diaminehaving a structure of Z which is added if necessary and atetracarboxylic anhydride, a dicarboxylic acid, a dicarboxylicdichloride, a dicarboxylic acid derivative or the like having astructure of Y, an amino group located at a terminal thereof ispreferably capped with an acid anhydride containing an aliphatic groupor a cyclic compound group having at least one group of an alkenyl groupand an alkynyl group.

[0028] E, that is, an aliphatic group or a cyclic compound group havingat least one group of an alkenyl group or an alkynyl group includes, forinstance:

[0029] but is not limited to these groups.

[0030] Particularly preferable E among these is selected from:

[0031] and two or more kinds of these may be used.

[0032] Further, Z of the polyamide resin represented by the generalformula (1) which is used if necessary includes, for instance:

[0033] but is not limited to these groups, and two or more kinds ofthese groups may be used.

[0034] The fraction b of Z of the general formula (1) to be used whenparticularly superior adhesion to a substrate such as a silicon wafer isrequired, is at most 40% by mole. It is not preferable to exceed 40% bymole, because solubility of the resin is badly decreased to generate adevelopment residue (scum) making a pattern processing infeasible.Incidentally, each of X, Y and Z to be used may be of one kind or amixture of two or more kinds thereof.

[0035] The photosensitive material (B) to be used in the presentinvention is a 1,2-naphthoquinone-2-diazide-5-sulfonate ester compoundor a 1,2-naphthoquinone-2-diazide-4-sulfonate ester compound of a phenolcompound having a skeletal structure represented by the general formula(5) below. An example in which a similar substance as represented by theformula (5) is used, has been disclosed in JP-A-2000-275833.

[0036] In spite of some effect to increase sensitivity obtained by usingthe above similar substance, further higher sensitivity has beenrequired in a recent shift of a coating film toward a thicker film. As aresult of studying various photosensitive materials considering thesesituations, it has been found that a1,2-naphthoquinone-2-diazide-5-sulfonate ester compound or a1,2-naphthoquinone-2-diazide-4-sulfonate ester compound of a phenolcompound having a skeletal structure represented by the formula (5) ofthe present invention brings about high sensitivity.

[0037] With regard to a degree of esterification of a1,2-naphthoquinone-2-diazide-5-sulfonate ester compound or a1,2-naphthoquinone-2-diazide-4-sulfonate ester compound of a phenolcompound having a skeletal structure represented by the formula (5) tobe used in the present invention, two or more moles of a1,2-naphthoquinone-2-diazide-5-sulfonic acid or a1,2-naphthoquinone-2-diazide-4-sulfonic acid are preferably esterifiedbased on one mole of the phenol compound. Three or more moles are morepreferably esterified.

[0038] An amount of the photosensitive material (B) to be added to thepolyamide (A) in the present invention is 1 to 50 parts by weight basedon 100 parts by weight of the polyamide. An amount to be added less thanthe lower limit impairs patterning ability of a resin, while an amountto be added more than the upper limit is not preferable because of muchdecreased sensitivity.

[0039] A dihydropyridine derivative can be added to the positive-workingphotosensitive resin composition of the present invention so as toimprove photosensitivity characteristics if necessary. Thedihydropyridine derivative includes, for instance,2,6-dimethyl-3,5-diacetyl-4-(2′-nitrophenyl)-1,4-dihydropyridine,4-(2′-nitrophenyl) -2,6-dimethyl-3,5-dicarboethoxy-1,4-dihydropyridineand4-(2′,4′-dinitrophenyl)-2,6-dimethyl-3,5-dicarbomethoxy-1,4-dihydropyridine.

[0040] It has been also found that a new effect is brought about by thephenol compound represented by the general formula (6) that can be usedin combination with the positive-working photosensitive resincomposition of the present invention. A molecular size of a1,2-naphthoquinone-2-diazide-5-sulfonate ester compound or a1,2-naphthoquinone-2-diazide-4-sulfonate ester compound of a phenolcompound having a skeletal structure represented by the formula (5) ofthe present invention is larger than that of a naphthoquinone diazidesulfonate ester compound generally used such as those shown below.

[0041] (wherein, Q is a hydrogen atom or selected from:

[0042] and at least one Q in each compound is the following groups:)

[0043] While a photosensitive material of larger molecular size canexert an ability to prevent dissolving in a wide range, there may be acase where a development residue (scum) is left at a pattern corner insome combination with the base resin, because solubility of thephotosensitive material of larger molecular size chemically changed byexposure is somewhat lower than that of the photosensitive material ofsmaller molecular size. In such a case, addition of a phenol compound ofsmaller molecular size can enhance overall solubility of thephotosensitive material to a developing solution resulting in higherresolution and sensitivity.

[0044] The phenol compound (C) represented by the general formula (6)includes those shown below, but is not limited to them.

[0045] An amount of the phenol compound (C) to be added is preferably 1to 30 parts by weight based on 100 parts by weight of the polyamiderepresented by the general formula (1). When an amount of the phenolcompound to be added exceeds the upper limit, there is a possibility ofa serious decrease of a film thickness retention rate as well asdeposition during refrigerated storage. When the amount to be added isless than the lower limit, there is a possibility of a decrease ofsensitivity in development.

[0046] Additives such as a leveling agent and a silane coupling agentcan be added to the positive-working photosensitive resin composition ofthe present invention if necessary.

[0047] These agents are dissolved in a solvent and used in a state ofvarnish in the present invention. The solvent includesN-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethylether, diethylene glycol dibutyl ether, propyrene glycol monomethylether, dipropyrene glycol monomethyl ether, propyrene glycol monomethylether acetate, methyl lactate, ethyl lactate, butyl lactate,methyl-1,3-butylene glycol acetate, 1,3-butylene glycol-3-monomethylether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate andthe like, and may be used solely or in a mixture.

[0048] With regard to a method for using the positive-workingphotosensitive resin composition of the present invention, first, saidcomposition is applied to a suitable base material, for instance, asilicon wafer, a ceramic substrate and an aluminum substrate. An amountto be coated is determined so that a final thickness of coating filmafter curing becomes 0.1 to 30 μm in the case of a semiconductor device.Film thickness of 0.1 μm or less makes it difficult to fully exert afunction as a surface protection film for a semiconductor element, andthe thickness of 30 μm or more not only makes it difficult to obtain afinely processed pattern but to lower throughput due to a prolongedprocessing time. A method for applying includes rotary film using aspinner, spray film using a spray coater, dipping, printing and rollfilm and the like.

[0049] Secondly, the coating film is dried by prebaking at 60 to 130° C.and then an actinic ray is irradiated in a desired pattern. An actinicray to be used includes X-ray, electron beam, ultraviolet ray, visibleray and the like, and has preferably a wavelength of 200 to 500 nm.

[0050] Thirdly, an exposed area is removed by dissolving with adeveloping solution to obtain a relief pattern. A developing solution tobe suitably used includes inorganic alkalis such as sodium hydroxide,potassium hydroxide, sodium carbonate, sodium silicate, sodiummetasilicate and aqueous ammonia, primary amines such as ethylamine andn-propylamine, secondary amines such as diethylamine anddi-n-propylamine, tertiary amines such as triethylamine andmethyldiethylamine, alcohol amines such as dimethy ethanol amine andtriethanol amine, an aqueous solution of alkalis such as a quaternaryammonium salt such as tetramethylammonium hydroxide andtetraethylammonium hydroxide and an aqueous solution obtained by addinga suitable amount of a water-soluble organic solvent such as methanoland ethanol or a surfactant to the above aqueous solution of alkalis. Asa method for developing, those such as spraying, paddling, dipping andsupersonic methods can be used.

[0051] Finally, a relief pattern formed by development is rinsed.Distilled water is used for rinsing. An oxazole ring and/or an imidering are then formed by a heat treatment to obtain a final pattern ofstout heat resistance.

[0052] A positive-working photosensitive resin composition of thepresent invention is useful not only for a semiconductor, but also foran interlayer insulation for a multilayered circuit, a cover coating fora flexible cupperclad plate, a solder resist film, a liquid crystalalignment layer and the like. Known processing steps can be used forother production steps of a semiconductor.

BEST MODE FOR CARRYING OUT THE INVENTION

[0053] The present invention will be specifically described by Exampleshereinbelow.

EXAMPLE 1 Synthesis of a Polyamide

[0054] A dicarboxylic acid derivative of 360.4 g (0.9 mol) obtained byreacting 0.9 mol of terephthalic acid, 0.1 mol of isophthalic acid and 2mol of 1-hydroxy-1,2,3-benzotriazole, and 366.3 g (1 mol) ofhexafluoro-2,2-bis(3-amino-4-hydroxy phenyl)propane were charged in afour-necked separable flask equipped with a thermometer, an agitator, afeed inlet and a dry nitrogen gas inlet tube, and added and dissolvedwith 3,000 g of N-methyl-2-pyrrolidone. The thus obtained mixture wasthen reacted at 75° C. in an oil bath for 12 hours.

[0055] The above mixture was then added with 32.8 g (0.2 mol) of5-norbornene-2,3-dicarboxylic anhydride dissolved in 500 g ofN-methyl-2-pyrrolidone and reacted for another 12 hours while stirring.After filtration, the reaction mixture was added to a solution ofwater/methanol of 3/1. A cake obtained by filtering a deposit was rinsedsufficiently with water and then dried under vacuum to obtain a desiredpolyamide (PA-1) represented by the general formula (1), wherein, X wasrepresented by the formula X-1 below, Y was a mixture of the formulaeY-1 and Y-2 below, a=100, and b=0.

Preparation of a Positive-Working Photosensitive Resin Composition

[0056] The synthesized polyamide (PA-1) of 100 g and 15 g of a1,2-naphthoquinone-2-diazide-4-sulfonate ester compound having astructure represented by the formula (Q-1) below were dissolved in 200 gof γ-butyrolactone and then filtrated using a 0.2 μm filter made of afluorocarbon resin to obtain a positive-working photosensitive resincomposition.

Evaluation of Characteristics

[0057] The obtained positive-working photosensitive resin compositionwas applied on a silicon wafer using a spincoater and then dried at 120°C. for 4 minutes using a hotplate to obtain a coating film of about 16μm thickness. The thus obtained coating film was exposed through a maskmade by TOPPAN PRINTING CO., LTD. (Test Chart No. 1: patterns forremaining and patterns for removing of 0.88 to 50 μm width weredepicted) using an i-line stepper NSR-4425i made by Nicon Corp., withvarious exposure amount. The silicon wafer was rinsed with pure waterfor 30 seconds after an exposed area of the composition was dissolvedand removed by dipping in a 2.38% aqueous solution oftetramethylammonium hydroxide for 80 seconds. As a result, it wasconfirmed that a pattern had been formed in an exposed area at theexposure amount of 620 mJ/cm² (sensitivity was 620 mJ/cm²). A filmthickness retention rate [(film thickness after development)/(filmthickness before development)×100] was 88.1% and a resolution was 8 μmwhich were satisfactory values. The coating film was then cured in aclean oven at 150° C./30 minutes and 320° C./30 minutes under acondition of an oxygen concentration of 1,000 ppm or less. A filmthickness after curing was 10.8 μm.

EXAMPLE 2

[0058] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that an amount of the photosensitivematerial (Q-1) added in Example 1 was changed to 10 g, and evaluatedsimilarly as in Example 1.

EXAMPLE 3

[0059] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that an amount of the photosensitivematerial (Q-1) added in Example 1 was changed to 20 g, and evaluatedsimilarly as in Example 1.

EXAMPLE 4

[0060] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that the photosensitive material (Q-1)in Example 1 was replaced with (Q-2), and evaluated similarly as inExample 1.

EXAMPLE 5

[0061] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that the photosensitive material (Q-1)in Example 1 was replaced with (Q-3), and evaluated similarly as inExample 1.

EXAMPLE 6

[0062] A polyamide (PA-2) represented by the general formula (1) whereinX was represented by the formula X-1 below; Y was represented by theformula Y-3 below; a=100, and b=0, was synthesized by using 1 mol ofdiphenylether-4,4′-dicarboxylic acid instead of 0.9 mol of terephthalicacid and 0.1 mol of isophthalic acid in the polyamide synthesis inExample 1. A positive-working photosensitive resin composition wasobtained similarly as in Example 1 except the above, and evaluatedsimilarly as in Example 1.

EXAMPLE 7

[0063] A polyamide (PA-3) represented by the general formula (1),wherein X was represented by the formula X-2 below; Y was represented bythe formula Y-3 below; a=100, and b=0, was synthesized by using 1 mol of3,3′-diamino-4,4′-dihydroxyphenylsulfone instead of hexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane. A positive-working photosensitiveresin composition was obtained similarly as in Example 1 except theabove, and evaluated similarly as in Example 1.

EXAMPLE 8

[0064] A mixture of 17.1 g (0.055 mol) of 4,4′-oxydiphthalic anhydride,13.0 g (0.110 mol) of 2-methyl-2-propanol and 10.9 g (0.138 mol) ofpyridine were charged in a four-necked separable flask equipped with athermometer, an agitator, a feed inlet and a dry nitrogen gas inlettube, and added and dissolved with 150 g of N-methyl-2-pyrrolidone.After 14.9 g (0.110 mol) of 1-hydroxy-1,2,3-benzotriazole and 30 g ofN-methyl-2-pyrrolidone were dropped in the reacted solution, 22.7 g(0.110 mol) of dicyclohexylcarbodiimide and 50 g ofN-methyl-2-pyrrolidone were dropped in the above solution and reacted ata room temperature overnight.

[0065] Subsequently, 27.1 g (0.055 mol) of a dicarboxylic acidderivative (activated ester) obtained by reacting 1 mol ofdiphenylether-4,4′-dicarboxylic acid and 2 mol of1-hydroxy-1,2,3-benzotriazole, 44.8 g (0.122 mol) ofhexafluoro-2,2-bis(3-amino-4-hydroxyphenyl)propane and 70 g ofN-methyl-2-pyrrolidone were added to the above reacted solution andstirred at a room temperature for 2 hours. Subsequently, the abovemixture was reacted similarly as in Example 1 except that the mixturewas reacted at 75° C. for 12 hours using an oil bath to synthesize apolyamide resin (PA-4) represented by the general formula (1), wherein Xwas represented by the formula X-1 below; Y was represented by theformulae Y-3 and Y-4 below. A positive-working photosensitive resincomposition was obtained similarly as in Example 1 except the above, andevaluated similarly as in Example 1.

EXAMPLE 9

[0066] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that the photosensitive material (Q-1)in Example 1 was replaced with (Q-4), and evaluated similarly as inExample 1.

COMPARATIVE EXAMPLE A

[0067] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that the1,2-naphthoquinone-2-diazide-4-sulfonate ester compound (Q-1) in Example1 was replaced with (Q-5), and evaluated similarly as in Example 1.

COMPARATIVE EXAMPLE B

[0068] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 6 except that the1,2-naphthoquinone-2-diazide-4-sulfonate ester compound (Q-1) in Example6 was replaced with (Q-5), and evaluated similarly as in Example 1.

COMPARATIVE EXAMPLE C

[0069] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that the photosensitive material (Q-1)in Example 1 was replaced with (Q-6), and evaluated similarly as inExample 1.

COMPARATIVE EXAMPLE 1

[0070] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that the photosensitive material (Q-1)in Example 1 was replaced with (Q-7), and evaluated similarly as inExample 1.

COMPARATIVE EXAMPLE 2

[0071] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 1 except that the photosensitive material (Q-1)in Example 1 was replaced with (Q-8), and evaluated similarly as inExample 1.

EXAMPLE 13

[0072] A mixture of 100 g of the polyamide resin (PA-1) used in Example1, 15 g of a 1,2-naphthoquinone-2-diazide-4-sulfonate ester compoundhaving a structure represented by the formula (Q-1) below and further 15g of a phenol (P-1) having the structure below was dissolved in 200 g ofγ-butyrolactone, and then filtrated with a 0.2 μm filter made of afluorocarbon resin to obtain a positive-working photosensitive resincomposition. The composition was evaluated similarly as in Example 1.

EXAMPLE 14

[0073] A mixture of 100 g of the polyamide resin (PA-2) used in Example6, 15 g of a 1,2-naphthoquinone-2-diazide-4-sulfonate ester compoundhaving a structure represented by the formula (Q-1) below and further 15g of a phenol (P-1) having the structure below was dissolved in 200 g ofγ-butyrolactone, and then filtrated with a 0.2 μm filter made of afluorocarbon resin to obtain a positive-working photosensitive resincomposition. The composition was evaluated similarly as in Example 1.

EXAMPLE 15

[0074] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 13 except that the phenol compound (P-1) inExample 13 was replaced with (P-2), and evaluated similarly as inExample 1.

COMPARATIVE EXAMPLE D

[0075] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 13 except that the1,2-naphthoquinone-2-diazide-4-sulfonate ester compound (Q-1) in Example13 was replaced with (Q-5), and evaluated similarly as in Example 1.

COMPARATIVE EXAMPLE E

[0076] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 14 except that the1,2-naphthoquinone-2-diazide-4-sulfonate ester compound (Q-1) in Example14 was replaced with (Q-5), and evaluated similarly as in Example 1.

COMPARATIVE EXAMPLE F

[0077] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 15 except that the1,2-naphthoquinone-2-diazide-4-sulfonate ester compound (Q-1) in Example15 was replaced with (Q-5), and evaluated similarly as in Example 1.

COMPARATIVE EXAMPLE 3

[0078] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 13 except that the1,2-naphthoquinone-2-diazide-4-sulfonate ester compound (Q-1) in Example13 was replaced with (Q-7), and evaluated similarly as in Example 1.

COMPARATIVE EXAMPLE 4

[0079] A positive-working photosensitive resin composition was obtainedsimilarly as in Example 13 except that the1,2-naphthoquinone-2-diazide-4-sulfonate ester compound (Q-1) in Example13 was replaced with (Q-8), and evaluated similarly as in Example 1.

[0080] (wherein, Q is a hydrogen atom or:

[0081] and 90% of total Q is:)

[0082] (wherein, Q is a hydrogen atom or:

[0083] and 100% of total Q is:)

[0084] (wherein, Q is a hydrogen atom or:

[0085] and 75% of total Q is:)

[0086] (wherein, Q is a hydrogen atom or:

[0087] and 90% of total Q is:)

[0088] (wherein, Q is a hydrogen atom or:

[0089] and 90% of total Q is:)

[0090] (wherein, Q is a hydrogen atom or:

[0091] and 90% of total Q is:)

[0092] (wherein, Q is a hydrogen atom or:

[0093] and 67% of total Q is:)

[0094] (wherein, Q is a hydrogen atom or:

[0095] and 70% of total Q is:)

[0096] Results of the evaluation in Examples 1 to 9, ComparativeExamples A, B and C, and Comparative Examples 1 to 2 are shown in Table1, and results of the evaluation in Examples 13 to 15 and ComparativeExamples D, E and F, and Comparative Examples 3 to 4 are shown in Table2. TABLE 1 Amount of Component Characteristics Photosensitive FilmThickness Polyamide (PA) Material (Q) Sensitivity Retention Rate*Resolution 100 g Amine Acid (g) (mJ/cm²) (%) (μm) Example 1 PA-1 X-1Y-1, Y-2 Q-1 15 620 88.1 8 Example 2 PA-1 X-1 Y-1, Y-2 Q-1 10 570 85.3 9Example 3 PA-1 X-1 Y-1, Y-2 Q-1 20 660 91.8 8 Example 4 PA-1 X-1 Y-1,Y-2 Q-2 15 630 89.7 8 Example 5 PA-1 X-1 Y-1, Y-2 Q-3 15 600 86.9 9Example 6 PA-2 X-1 Y-3 Q-1 15 630 87.3 8 Example 7 PA-3 X-2 Y-3 Q-1 15590 86.9 8 Example 8 PA-4 X-1 Y-3, Y-4 Q-1 15 630 87.7 8 Example 9 PA-1X-1 Y-1, Y-2 Q-4 15 850 87.7 7 Comparative PA-1 X-1 Y-1, Y-2 Q-5 15 69085.2 12 Example A Comparative PA-2 X-1 Y-3 Q-5 15 710 85.9 10 Example BComparative PA-1 X-1 Y-1, Y-2 Q-6 15 880 85.9 10 Example C ComparativePA-1 X-1 Y-1, Y-2 Q-7 15 810 83.2 13 Example 1 Comparative PA-1 X-1 Y-1,Y-2 Q-8 15 790 84.3 12 Example 2

[0097] TABLE 2 Amount of Component Characteristics Photosensitive PhenolFilm Thickness Polyamide (PA) Material (Q) Compound (P) SensitivityRetention Resolution 100 g Amine Acid (g) (g) (mJ/cm²) Rate* (%) (μm)Example 13 PA-1 X-1 Y-1, Y-2 Q-1 15 P-1 15 480 82.2 3 Example 14 PA-2X-1 Y-3 Q-1 15 P-1 15 450 82.9 3 Example 15 PA-1 X-1 Y-1, Y-2 Q-1 15 P-215 440 82.6 4 Comparative PA-1 X-1 Y-1, Y-2 Q-5 15 P-1 15 550 81.8 6Example D Comparative PA-2 X-1 Y-3 Q-5 15 P-1 15 540 80.1 6 Example EComparative PA-1 X-1 Y-1, Y-2 Q-5 15 P-2 15 520 79.7 6 Example FComparative PA-1 X-1 Y-1, Y-2 Q-7 15 P-1 15 590 81.5 7 Example 3Comparative PA-1 X-1 Y-1, Y-2 Q-8 15 P-1 15 570 81.7 7 Example 4

EXAMPLE 19

[0098] The positive-working photosensitive resin composition used inExample 1 was applied on a silicon wafer using a spincoater, and thendried at 90° C. for 30 minutes in a box-type oven to obtain a coatingfilm of about 50 μm thickness. The thus obtained coating film wasexposed with an exposure amount of 3,000 mJ through a mask made byTOPPAN PRINTING CO., LTD. (Test Chart No. 1: patterns for remaining andpatterns for removing of 0.88 to 50 μm width were depicted) usingMaskaligner PLA-600F made by CANON Inc. After the coating film in theexposed area was dissolved and removed by dipping in a 2.38% aqueoussolution of tetramethylammonium hydroxide for 150 seconds, the siliconwafer was then rinsed with pure water for 30 seconds. As a result, itwas confirmed that a pattern of 40 μm had been formed. A film thicknessretention rate [(film thickness after development)/(film thicknessbefore development)×100] was 80.4%. The coating film was then cured in aclean oven at 150° C./30 minutes and 320° C./30 minutes under acondition of an oxygen concentration of 1,000 ppm or less. Filmthickness after curing was 28.8 μm.

COMPARATIVE EXAMPLE 5

[0099] The positive-working photosensitive resin composition used inExample 1 was applied on a silicon wafer using a spincoater, and thendried at 90° C. for 30 minutes in a box-type oven to obtain a film ofabout 50 μm thickness. The thus obtained film was exposed with anexposure amount of 3,000 mJ through a mask made by TOPPAN PRINTING CO.,LTD. (Test Chart No. 1: patterns for remaining and patterns for removingof 0.88 to 50 μm width were depicted) using Maskaligner PLA-600F made byCANON Inc. It took as long as 170 seconds to remove the coating film ofa pattern using a 2.38% aqueous solution of tetramethylammoniumhydroxide. Similarly, the silicon wafer was rinsed with pure water for30 seconds. As a result, it was confirmed that a pattern of 60 μm hadbeen formed. A film thickness retention rate [(film thickness afterdevelopment)/(film thickness before development)×100] was 72.1%. Thecoating film was then cured in a clean oven at 150° C./30 minutes and320° C./30 minutes under a condition of an oxygen concentration of 1,000ppm or less. Film thickness after curing was 25.2 μm, which was a littlethinner than that in Example 19.

[0100] As apparent from the Examples above, according to the presentinvention, a positive-working photosensitive resin composition with highsensitivity that can form a pattern of a high resolution and a high filmthickness retention rate even in an increased film thickness whilekeeping conventional characteristics, can be obtained.

INDUSTRIAL APPLICABILITY

[0101] A positive-working photosensitive resin composition of thepresent invention is useful not only for a semiconductor, but also foran interlayer insulation for a multilayered circuit, a cover coating fora flexible cupperclad plate, a solder resist film, a liquid crystalalignment layer and the like.

1. (amended) A positive-working photosensitive resin compositioncharacterized by comprising 100 parts by weight of a polyamide (A)represented by the general formula (1):

[wherein, X is a cyclic compound group of 2 to 4 valences that may havea hydroxyl group or a group wherein a hydrogen atom of a hydroxyl groupis replaced with an organic group having 1 to 20 carbon atoms; Y is acyclic compound group of 2 to 4 valences that may have a hydroxyl group,a group wherein a hydrogen atom of a hydroxyl group is replaced with anorganic group having 1 to 20 carbon atoms, a carboxyl group or a groupwherein a hydrogen atom of a hydroxyl group is replaced with an organicgroup having 1 to 20 carbon atoms; and Z is:

(wherein, each of R₁ and R₂ is a bivalent organic group; each of R₃ andR₄ is a univalent organic group); a and b each shows a molar fraction;a+b=100% by mole; a=60 to 100% by mole; b=0 to 40% by mole)]; and 1 to50 parts by weight of a photosensitive material (B), that is, a1,2-naphthoquinone-2-diazide-5-sulfonate ester compound or a1,2-naphthoquinone-2-diazide-4-sulfonate ester compound of a phenolcompound having a skeletal structure represented by the general formula(5):


2. The positive-working photosensitive resin composition according toclaim 1, wherein a polyamide (A) is represented by the general formula(3):

[wherein, X is a tetravalent cyclic compound group; Y is a divalentcyclic compound group; Z is:

(wherein, each of R₁ and R₂ is a bivalent organic group; each of R₃ andR₄ is a univalent organic group); E is an aliphatic group or a cycliccompound group having at least one group of an alkenyl group or analkynyl group; a and b each shows a molar fraction; a+b=100% by mole;a=60 to 100% by mole; b=0 to 40% by mole; n=2⁻ to 500)].
 3. (cancelled)4. (cancelled)
 5. (amended) The positive-working photosensitive resincomposition according to claim 1 or 2 further comprising 1 to 30 partsby weight of a phenol compound (C) represented by the general formula(6):

(wherein, each of R₁₁, R₁₂, R₁₃ and R₁₄ is selected from a hydrogenatom, a halogen atom, an alkyl group, an alkoxy group and a cycloalkylgroup, and may be the same or different from each other; p is an integerof 0 to 3; q is an integer of 0 to 3.; p+q≧2; R₁₅ is selected from asingle bond, a methylene group, an alkylene group, an oxygen atom, acarbonyl group, a carbonyl ether group, a sulfur atom, a sulfonyl groupand an azo group); based on 100 parts by weight of a polyamide (A)represented by the general formula (1) or the general formula (3). 6.The positive-working photosensitive resin composition according to claim1, wherein X in a polyamide represented by the general formula (1) isselected from the groups below: (wherein, each of R₁₁, R₁₂, R₁₃ and R₁₄is selected from a hydrogen atom, a halogen atom, an alkyl group, analkoxy group and a cycloalkyl group, and may be the same or differentfrom each other; p is an integer of 0 to 3; q is an integer of 0 to 3;p+q≧2; R₁₅ is selected from a single bond, a methylene group, analkylene group, an oxygen atom, a carbonyl group a carbonyl ether group,a sulfur atom, a sulfonyl group and an azo group); based on 100 parts byweight of a polyamide (A) represented by the general formula (1) or thegeneral formula (3).
 6. The positive-working photosensitive resincomposition according to claim 1, wherein X in a polyamide representedby the general formula (1) is selected from the groups below:

(wherein, each of R₁₆ is selected from a hydrogen atom, an alkyl group,an alkoxy group, an alkyl ester group and a halogen atom, and may be thesame or different from each other; r is an integer of 0 to 2).
 7. Thepositive-working photosensitive resin composition according to claim 2,wherein X in a polyamide represented by the general formula (3) isselected from the groups below.


8. The positive-working photosensitive resin composition according toclaim 1, wherein Y in a polyamide represented by the general formula (1)is selected from the groups below:

(wherein, each of R₁₆is selected from a hydrogen atom, an alkyl group,an alkoxy group, an alkyl ester group and a halogen atom, and may be thesame or different from each other; r is an integer of 0 to 2).
 9. Thepositive-working photosensitive resin composition according to claim 2,wherein Y in a polyamide represented by the general formula (3) isselected from the groups below:

(wherein, each of R₁₆ is selected from a hydrogen atom, an alkyl group,an alkoxy group, an alkyl ester group and a halogen atom, and may be thesame or different from each other; r is an integer of 0 to 2).
 10. Thepositive-working photosensitive resin composition according to claim 1,wherein a terminal group of a polyamide represented by the generalformula (1) is bonded with an aliphatic group or a cyclic compound grouphaving at least one group of an alkenyl group or an alkynyl group. 11.The positive-working photosensitive resin composition according to claim1 or 2, wherein a terminal group of a polyamide represented by thegeneral formula (1) or the general formula (3) is selected from thegroups below.


12. The positive-working photosensitive resin composition according toclaim 5, wherein a terminal group of a polyamide represented by thegeneral formula (1) or the general formula (3) is selected from thegroups below.


13. A semiconductor device manufactured by using the positive-workingphotosensitive resin composition according to claim 1 or
 2. 14. Asemiconductor device manufactured by using the positive-workingphotosensitive resin composition according to claim
 5. 15. Asemiconductor device obtained by applying the positive-workingphotosensitive resin composition according to claim 1 or 2 on asemiconductor element so that a film thickness of said positive-workingphotosensitive resin composition becomes 0.1 to 30 μm after heating,dehydration and cyclization, followed by prebaking, exposing, developingand heating.
 16. A semiconductor device obtained by applying thepositive-working photosensitive resin composition according to claim 5on a semiconductor element so that a film thickness of saidpositive-working photosensitive resin composition becomes 0.1 to 30 μmafter heating, dehydration and cyclization, followed by prebaking,exposing, developing and heating.